Resaturation of gas into a liquid feedstream

ABSTRACT

A method for enabling gas exchange and chemical reactions with one or more liquid streams contained in a reactive process vessel are provided. One or more exchange layers within the process vessel can be composed of both collector media and releaser media. The exchange layers allow elements to facilitate increased performance of vessel operations by promoting gas component mixing and diffusion. Improved rates of gas component exchange mean less coking and more gas components available for reaction.

RELATED APPLICATIONS

This application claims the benefit, and priority benefit, of U.S.Provisional Patent Application Ser. No. 62/951,681, filed Dec. 20, 2019,the disclosure and contents of which are incorporated by referenceherein in their entirety.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The presently disclosed subject matter relates generally to reactiveprocess vessels, and more specifically, to enabling the gas exchange andchemical reactions with one or more liquid streams or phases containedin reactive process vessels.

2. Description of the Prior Art

Process vessels in the field are often vertical cylindricalconstructions with fluid streams or phases which enter, pass through andexit such vessels. Industrial vessels are 6 inches to over 20 feet indiameter and 2 to over 100 feet high. The vessels containing reactivesystems can be used to promote chemical reactions.

Contained within many conventional vessels are different phases ofmaterials. A solid phase includes one or more beds of solid elements.Other phases contained in vessels include fluid phases including one ormore liquid phases and one or more gas phases. Multiple fluid phases canbe contained in a fluid stream. The state of the phases can depend ontheir operating conditions. Typical liquid throughput to a vessel ismeasured in barrels per day. Typical gas volumes are measured instandard cubic feet (SCF). The throughput of gas to a vessel istypically measured in standard cubic feet per barrel of liquid feed.

Improvements in this field are needed.

SUMMARY

In accordance with the presently disclosed subject matter, variousillustrative embodiments of a method for enabling the gas exchange andchemical reactions with one or more liquid streams contained in areactive process vessel are provided herein.

In certain illustrative embodiments, a method of treating areactant-lean liquid phase in a process vessel is provided. Thereactant-lean liquid phase and a gas phase can be passed co-currentlythrough an exchange layer in the process vessel. The gas phase comprisesa reactant. At least some of the reactant from the gas phase can bediffused into the reactant-lean liquid phase in the exchange layer toform a reactant-rich liquid phase. The exchange layer can include aplurality of collector media and a plurality of releaser media, and thecollector media can include porous solid materials capable of collectingthe reactant-lean liquid phase within the collector media. The releasermedia can include solid materials having a thin film formed on an outersurface thereof that is capable of facilitating contact and diffusionbetween the reactant-lean liquid phase and the gas phase. The thin filmcan be formed on the releaser media during processing as a result ofliquid released from the collected liquid phase. The process vessel canbe a trickle bed reactor. In certain aspects, the reactant-rich liquidphase can be passed through a bed of porous solid elements following theexchange layer. The porous solid elements can include at least one ofcatalysts, sorbents and reactants. A treating process can be performedin the process vessel to remove an undesired species from the liquidphase. The treating process can include at least one ofhydro-desulfurization, hydro-denitrogenation, hydro-cracking,hydrogenation, hydro-dearomatization, hydro-deoxygenation,hydro-demetallization, and isomerization. The undesired species caninclude at least one of sulfur, nitrogen, oxygen, aromatics, olefins,nickel, vanadium, iron, silicon or arsenic. The reactant-rich liquidphase can include at least one of naphtha, gasoline, kerosene, jet,diesel, gas oils, vegetable oils, animal tallow, and liquid water. Thereactant diffused from the gas stream into the reactant-lean liquidstream can include at least one of methane, butane, propane, butalene,propylene, hydrogen, ammonia, hydrogen sulfide, carbon dioxide, carbonmonoxide, sulfur oxides, nitrogen oxides, water gas, oxygen, andnitrogen. The releaser media can include at least one of catalysts,sorbents and reactants. In certain aspects, the size of the releasermedia can be no more than one-fourth the size of the collector media. Incertain aspects, each of the collector media in the exchange layer canhave at least twenty contact points on its outer surface that arecontacted by releaser media.

In certain illustrative embodiments, a method of treating a product-richliquid phase in a process vessel is also provided. The product-richliquid phase and a gas phase can be passed co-currently through anexchange layer in the process vessel, wherein the product-rich liquidphase can include a reaction product. At least some of the reactionproduct from the product-rich liquid phase can be diffused into the gasin the exchange layer to form a product-lean liquid phase. The exchangelayer can include a plurality of collector media and a plurality ofreleaser media, and wherein the collector media comprise porous solidmaterials capable of collecting the product-rich liquid phase within thecollector media. The releaser media can include solid materials that arecapable of facilitating contact and diffusion between the product-richliquid phase and the gas phase. In certain aspects, the size of thereleaser media can be no more than one-fourth the size of the collectormedia. In certain aspects, each of the collector media in the exchangelayer can have at least twenty contact points on its outer surface thatare contacted by releaser media. The process vessel can be a trickle bedreactor. In certain aspects, the product-lean liquid phase can be passedthrough a bed of porous solid elements following the exchange layer. Theporous solid elements can include at least one of catalysts, sorbentsand reactants. A treating process can be performed in the process vesselto remove an undesired species from the liquid phase. The treatingprocess can include at least one of hydro-desulfurization,hydro-denitrogenation, hydro-cracking, hydrogenation,hydro-dearomatization, hydro-deoxygenation, hydro-demetallization, andisomerization. The undesired species can include at least one of sulfur,nitrogen, oxygen, aromatics, olefins, nickel, vanadium, iron, silicon orarsenic. The product-lean liquid phase can include at least one ofnaphtha, gasoline, kerosene, jet, diesel, gas oils, vegetable oils,animal tallow, and liquid water. The releaser media can include at leastone of catalysts, sorbents and reactants.

In certain illustrative embodiments, a method of treating areactant-lean, product-rich liquid phase in a trickle bed process vesselis also provided. A reactant-lean, product-rich liquid phase and a gasphase can be passed co-currently through an exchange layer in thetrickle bed process vessel. The gas phase can include a reactant. Atleast some of the reaction products from the reactant-lean, product-richliquid phase can be diffused into the gas phase and at least some of thereactant from the gas phase can be diffused into the reactant-lean,product-rich liquid phase in the exchange layer to form a reactant-rich,product-lean liquid phase. The exchange layer can include a plurality ofcollector media and a plurality of releaser media. The collector mediacan include porous solid materials capable of collecting thereactant-lean liquid phase within the collector media. The releasermedia can include solid materials having a thin film formed on an outersurface thereof that is capable of facilitating contact and diffusionbetween the reactant-lean, product-rich liquid phase and the gas phase.The thin film is can be formed on the releaser media during processingas a result of liquid released from the collected liquid phase. Incertain aspects, the reactant-rich, product-lean liquid phase can passthrough a bed of porous solid elements following the exchange layer. Theporous solid elements can include at least one of catalysts, sorbentsand reactants. A treating process can be performed in the process vesselto remove an undesired species from the liquid phase, wherein thetreating process can include at least one of hydro-desulfurization,hydro-denitrogenation, hydro-cracking, hydrogenation,hydro-dearomatization, hydro-deoxygenation, hydro-demetallization, andisomerization. The undesired species can include at least one of sulfur,nitrogen, oxygen, aromatics, olefins, nickel, vanadium, iron, silicon orarsenic. The reactant-rich, product-lean liquid phase can include atleast one of naphtha, gasoline, kerosene, jet, diesel, gas oils,vegetable oils, animal tallow, and liquid water. The reactant diffusedfrom the gas stream into the reactant-lean, product-rich liquid streamcan include at least one of methane, butane, propane, butalene,propylene, hydrogen, ammonia, hydrogen sulfide, carbon dioxide, carbonmonoxide, sulfur oxides, nitrogen oxides, water gas, oxygen, andnitrogen. The releaser media can include at least one of catalysts,sorbents and reactants. In certain aspects, the size of the releasermedia can be no more than one-fourth the size of the collector media. Incertain aspects, each of the collector media in the exchange layer canhave at least twenty contact points on its outer surface that arecontacted by releaser media.

In certain illustrative embodiments, a trickle bed process vessel fortreatment of a reactant-lean, product-rich liquid stream is provided.The process vessel can include an exchange layer having a plurality ofcollector media and a plurality of releaser media, wherein the exchangelayer is capable of facilitating diffusion of one or more reactants froma gas phase into a reactant-lean, product-rich liquid phase within theexchange layer to form a reactant-rich, product-lean liquid phase. Theprocess vessel can also include a treatment layer downstream of theexchange layer having a bed of porous solid elements, the porous solidelements having at least one of catalysts, sorbents and reactants andcapable of performing a treating process to remove an undesired speciesfrom the liquid phase, wherein the treating process can include at leastone of hydro-desulfurization, hydro-denitrogenation, hydro-cracking,hydrogenation, hydro-dearomatization, hydro-deoxygenation,hydro-demetallization, and isomerization. In certain aspects, thecollector media and the releaser media can be packed within the exchangelayer such that each of the collector media has at least twenty contactpoints on its outer surface that are contacted by releaser media. Thegas phase and the reactant-lean, product-rich liquid phase can undergoco-current flow within the exchange layer. The collector media caninclude porous solid materials capable of collecting the reactant-leanliquid phase within the collector media. The releaser media can includesolid materials having a thin film formed on an outer surface thereofthat is capable of facilitating contact and diffusion between thereactant-lean, product-rich liquid phase and the gas phase. The thinfilm can be formed on the releaser media during processing as a resultof liquid released from the collected liquid phase. In certain aspects,the releaser media can include at least one of catalysts, sorbents andreactants. In certain aspects, the size of the releaser media can be nomore than one-fourth the size of the collector media. The undesiredspecies can be at least one of sulfur, nitrogen, oxygen, aromatics,olefins, nickel, vanadium, iron, silicon or arsenic, and thereactant-rich, product-lean liquid phase can be at least one of naphtha,gasoline, kerosene, jet, diesel, gas oils, vegetable oils, animaltallow, and liquid water, and the reactant diffused from the gas streaminto the reactant-lean, product-rich liquid stream can be at least oneof methane, butane, propane, butalene, propylene, hydrogen, ammonia,hydrogen sulfide, carbon dioxide, carbon monoxide, sulfur oxides,nitrogen oxides, water gas, oxygen, and nitrogen.

BRIEF DESCRIPTION OF THE DRAWINGS

Some of the features and benefits of the present invention having beenstated, others will become apparent as the description proceeds whentaken in conjunction with the accompanying drawings, in which:

FIG. 1 is a side view of process vessels having a plurality of layers orzones in accordance with illustrative embodiments of the presentlydisclosed subject matter.

FIG. 2 is a side view of process vessels having a plurality of layers orzones in accordance with illustrative embodiments of the presentlydisclosed subject matter.

FIG. 3A and FIG. 3B are comparison views of liquid and gas co-currentflow through an exchange layer and an exchange layer spanning a bed in aprocess vessel in accordance with illustrative embodiments of thepresently disclosed subject matter.

FIG. 4 is a side view of an exchange layer in accordance with anillustrative embodiment of the presently disclosed subject matter.

FIG. 5A is a side view of collector media and releaser media inaccordance with an illustrative embodiment of the presently disclosedsubject matter.

FIG. 5B is a side view of collector media and releaser media with thinfilm formed thereon in accordance with an illustrative embodiment of thepresently disclosed subject matter.

FIG. 6 is a side view of releaser media with thin film formed thereon inaccordance with an illustrative embodiment of the presently disclosedsubject matter.

FIG. 6A is a side view of releaser media with thin film formed thereonand an active site in accordance with an illustrative embodiment of thepresently disclosed subject matter.

FIG. 6B is a side view of releaser media with thin film formed thereonin accordance with an illustrative embodiment of the presently disclosedsubject matter.

FIG. 6C is a side view of collector media and releaser media with thinfilm formed thereon in accordance with an illustrative embodiment of thepresently disclosed subject matter.

FIG. 7 is a side view of filled collector media surrounded by releasermedia in accordance with an illustrative embodiment of the presentlydisclosed subject matter.

FIG. 8 is a side view of partially filled collector media surrounded byreleaser media in accordance with an illustrative embodiment of thepresently disclosed subject matter.

FIG. 9 is a three dimensional perspective view of a collector pane witha plurality of perforation holes in accordance with an illustrativeembodiment of the presently disclosed subject matter.

FIG. 10 is a three dimensional perspective view of a collector pane witha plurality of perforation holes in accordance with an illustrativeembodiment of the presently disclosed subject matter.

FIG. 11 is a comparison view of a prior art process vessel and a processvessel in accordance with an illustrative embodiment of the presentlydisclosed subject matter.

FIG. 12 is a side view of a process vessel in accordance with anillustrative embodiment of the presently disclosed subject matter.

FIG. 13 is a side view of a stratified exchange layer in accordance withan illustrative embodiment of the presently disclosed subject matter.

FIG. 14A is a three dimensional view of releaser media surroundingcollector media in accordance with an illustrative embodiment of thepresently disclosed subject matter.

FIG. 14B is a three dimensional cross-sectional view of releaser mediasurrounding collector media in accordance with an illustrativeembodiment of the presently disclosed subject matter.

While the presently disclosed subject matter will be described inconnection with the preferred embodiment, it will be understood that itis not intended to limit the presently disclosed subject matter to thatembodiment. On the contrary, it is intended to cover all alternatives,modifications, and equivalents, as may be included within the spirit andthe scope of the presently disclosed subject matter as defined by theappended claims.

DETAILED DESCRIPTION

In accordance with the presently disclosed subject matter, variousillustrative embodiments of a method for enabling the gas exchange andchemical reactions with one or more liquid streams contained in areactive process vessel are provided herein.

In certain illustrative embodiments, as shown in FIGS. 1-14, multi-phasereactions can occur within a process vessel 100. One or morereactant-containing feed gas components can be diffused into one or morefeed liquids containing undesired species. These diffused phases can bepassed over one or more element beds 120 disposed in the vessel 100. Theone or more diffused fluid phases can be contacted with active sites 40within the one or more element beds 120 in the vessel 100. Active sites40 typically include one or more of catalyst sites, sorbent sites andreactant sites.

Element beds 120 can contain one or more elements 125. Elements 125 aretypically porous solid materials. Elements 125 can be non-porous solidmaterials. Elements 125 can be one or more of catalysts, sorbents, andreactants. Elements 125 are typically 1/32″ to 1.5″ in size and can bepacked in beds. Elements 125 can contain or hold active featureshereinafter called active sites 40. Active sites 40 are one or more ofcatalyst sites, sorbent sites, and reactant sites. The external surfacearea of elements 125 is typically in the range of 100 to 800 square feetper cubic foot of element beds 120.

As shown in FIG. 1, elements 125 in element beds 120 can all be thesame, or elements beds 120A, 120B, 120C etc, can have different types orsizes of elements 125, or various combinations thereof throughout vessel100, according to various illustrative embodiments.

Porous elements 125 can be comprised of micropores, mesopores and/ormacropores. Micropores have diameters less than 2 nanometers. Mesoporeshave diameters between 2 nanometers and 50 nanometers. Macropores havediameters larger than 50 nanometers. Elements 125 can contain otherporous features with diameters up to 300 nanometers. Under appropriateoperating conditions, the element beds 120 allow reactions to removeundesired species from the diffused fluid, create species-free liquidproduct, and create other products from the reaction between thegas-diluted phase and the undesired liquid species.

In certain illustrative embodiments, components of the presentlydisclosed subject matter can include one or more of: element beds 120containing active sites 40 disposed in the vessel 100;reactant-containing gas phases fed to the vessel 100; undesiredspecies-containing liquid phases fed to the vessel 100; solutions of gasand liquid feed contacted with element beds 120; species-free liquidproducts formed on the active sites 40; other products formed on theactive sites 40 from reaction of gas components with undesired liquidspecies; remaining feed gas phases recovered for recycle or subsequentprocessing; other products recovered for subsequent processing; andliquid products free of undesired species.

Efficient operation of vessel 100 relies on effective mixing. For liquidand gas phase flows, mixing refers to any operation used to combine thephases. Agitation is a common method of mixing, which forces fluids tocombine by mechanical means. Mixing fluids increases diffusion orexchange of components between them. Diffusion of fluid components is awell-known phenomenon. Diffusion from a region of high concentration toone of low concentration is defined by Ficks' laws, (see Adolph Ficks,1855). Ficks' laws state that high-concentration components present in afluid can diffuse into fluid containing little-to-no amounts of the samecomponents. Ficks' laws also state that the rate of change inconcentration of a component across a fluid-fluid boundary isproportional to the surface area of that boundary. A reduction ininterfacial surface area between two phases can reduce the speed withwhich one phase can diffuse into another.

In accordance with the presently disclosed subject matter, it isdesirable to have high interfacial surface area between the liquid andgas phases at the interface of elements 125 in vessels 100 to createsufficient exchange between the phases. The gas exchange is important tocreate conditions which are suitable for desirable reactions.

A gas phase which partially dissolves into a liquid phase creates agas-liquid solution. The maximum amount of dissolved gas in the liquidphase depends on the saturation limits. Higher pressures and lowertemperatures promote increased saturation limits. Saturation isdetermined by the diffusion rate of the gas into the liquid. Thediffusion rate can have an influence on the reaction kinetics whichrequires the simultaneous presence of active sites 40, liquid reactants,and gas reactants to form products. Reaction kinetics define the rate atwhich a particular reaction occurs. Higher concentration of dissolvedgas in the liquid phase is desired in order to promote desiredreactions.

In accordance with the presently disclosed subject matter, high rates ofdiffusion can occur in vessels 100 when one or more high-concentrationgas phase components mix with one or more liquid phase materials thatcontain little or none of the same components. A liquid phase with a lowconcentration of dissolved, reactive gas relative to the solubilitylimits can be called a “reactant-lean” liquid phase. A liquid phase witha high concentration of dissolved, reactive gas relative to thesaturation limits can be called a “reactant-rich” liquid phase.Reactant-lean liquid phases can occur in the original liquid streams fedto the vessel 100 or can be due to depletion of the one or moredissolved gases in the one or more liquid phases during interaction withactive sites 40. Within a given process vessel 100, a reactant-richliquid phase has more gas-based reactant dissolved in the liquid phasewhen compared to a reactant-lean liquid phase. Reactant-lean liquidphases are less capable of producing a desired reaction compared toreactant-rich liquid phases. One or more products can be created as aresult of reaction with active sites 40. Desirable reactions can reduceundesired species by converting reactants within reactant-rich liquidphases to products. Some of these products are gases dissolved in theliquid phase. These dissolved gas products are herein called “reactionproducts.” Reaction products are released from active sites 40 into theliquid phase. Reaction products can exist as a solute in the liquidphase and can interfere with reactions between gas phase reactant andundesired species, resulting in a reduced rate of desirable reactions. Aliquid phase with higher concentrations of one or more reaction productscan be called a “product-rich” liquid phase. Where a product-rich liquidphase forms, a concentration gradient of reaction products can bedeveloped between the liquid and gas phases and diffusion of reactionproducts into the surrounding gas phase can be promoted. Where aproduct-rich liquid phase forms, desirable reaction rates can bereduced. It is desirable to remove these reaction products from theliquid phase via gas exchange of reaction products. Liquid phases withrelatively low concentrations of reaction products can be called a“product-lean” liquid phase. Product-lean liquid phases can be morecapable of producing a desirable reaction compared to product-richliquid phases because less reaction products interfere with thereactions between undesired species and dissolved gas reactants. Liquidphases can be described as reactant-rich or reactant-lean andproduct-rich or product-lean liquid phases.

In accordance with the presently disclosed subject matter, one or moreliquid phases fed to a vessel 100 contain undesired species to bemitigated or converted within the process. One or more gas componentscan be mixed with feed liquid phases by diffusion and gas exchange.Exchanged gas feed can contain one or more reactant components capableof mitigating the undesired species in the liquid phase. Mitigation canbe performed at and by the active sites 40 contained in element beds120. These active sites 40 help to promote reactions to remove undesiredspecies from the liquid phase. As a result of the promoted reactions,reaction products can be generated which become a part of the liquid andgas flow of the vessel 100. In a conversion process where reactants,including active sites 40 and fluid components, are freely available tointeract with each other, conversion can take place at the speed of themolecular interaction between the reactants, typically defined as therate of reaction.

In traditional multiphase reactors, a number of steps must proceed inorder for the desired reaction to occur: one or more gas and liquidphases must be supplied as feeds to the vessel; one or more gas phasecomponent reactants must diffuse into the one or more liquid phasereactants; active sites 40 must be available to undertake reaction; oneor more diffused gas reactants and one or more liquid phase reactantsmust react together at the active sites 40.

The reactor's overall rate of reaction will be limited to the slowestrate in the steps described above. For many but not all typical processvessels, the rate of diffusion of one or more gas phase reactants intoone or more liquid phase reactants is typically the rate-limiting step.As described previously, Ficks' laws dictate this rate of diffusion isdependent on the interfacial surface area between the liquid phase andthe gas phase. A reduced rate of diffusion can be an impediment toprocess vessel operation.

In accordance with the presently disclosed subject matter, it isdesirable to have an inter-fluid phase surface area for element beds 120within vessel 100 as large as possible to promote diffusion rates. Thiscan create reaction-rich, product-lean liquids and will lead to higherreaction rates.

While introduced together, the one or more liquid and gas phases canhave varying velocities, temperatures, pressures, and components in thevessel and within the bed of elements 120. The flows of liquid phasesthrough the element beds 120 are largely driven by gravity while the gasphase flows are largely driven by the pressure differential between theinlet and outlet of the vessel. The gas phase can also experience a dragforce due to boundary conditions at the liquid-gas interface. Theretarding force on the gas phase can increase the amount of pressuredifferential required to push the gas phase through the vessel and itselement beds 120. The liquid phase can feel an equal and opposite forcefrom the gas phase. The transportive forces on the liquid phases are thesum of gravity and the drag force. As the fluid phases move deeper intothe bed or vessel, the liquid and gas phases can attempt to arrangethemselves in a way which minimizes the pressure differential across thebed or vessel. This arrangement tends to increase the separation ofliquid and gas phase volumes, which can reduce the interfacial surfacearea between the two phases. Reduction of surface area and increase ofliquid-gas phase volume separation can continue and can grow as thefluids move deeper into the bed or vessel.

In accordance with Ficks' laws, larger surface areas between liquid andgas phases characterize well-mixed liquid and gas phases as well asgreater diffusion or exchange of molecules between the phases. Smallersurface areas between liquid and gas phases can characterize poorlymixed liquid and gas phases as well as lesser diffusion or exchange ofmolecules between the two phases. The reduction of liquid-gas surfaceinterface can result in reduced amounts of gas reactant moving into theliquid phase, limiting the effectiveness of the element bed 120 orvessel 100. Reduced diffusion between fluid phases can retard exchangebetween the liquid and gas. This leads to reactant-rich, product-leanliquids transitioning to reactant-lean, product-rich liquids as thephases flow through the vessel. This is not a desirable transition.

There are many different vessel types. These can be regarded asreactors, separators, guard vessels, or sorbent beds. In certainillustrative embodiments a reactor is a type of trickle bed processvessel. A large variety of treating processes exist in different typesof vessels. Many of these are hydro-treaters. Examples of processes arehydro-desulfurization, hydro-denitrogenation, hydro-cracking,hydrogenation, hydro-dearomatization, hydro-deoxygenation,hydro-demetallization, isomerization, and other industrial processes.Unit types in refining and petrochemical applications can be naphthahydro-treaters, PyGas hydro-treaters, reformers, diesel hydro-treaters,gas oil hydro-treaters, cat feed hydro-treaters, FCC Gasolinehydro-treaters, FCC hydrogenation units, renewable dieselhydro-treaters, fixed-bed transesterification vessels, hydro-crackerpre-treaters, hydro-crackers, isomerization units, kerosenehydro-treaters, jet hydro-treaters, lube oil hydro-treaters, de-waxingunits, resid hydro-treaters, dryers, chloride treaters, clay treaters,salt dryers, and other fixed bed units.

Liquid streams can be organic or inorganic. Common liquid phases includevegetable oils, animal tallow, water, hydrocarbons, crude oil andderivatives of crude oil such as naphtha, gasoline, kerosene, jet,diesel, gas oil, or other crude oil derivatives. Common gas phasesinclude methane, butane, propane, hydrogen, ammonia, hydrogen sulfide,hydrogen chloride, carbon dioxide, carbon monoxide, sulfur oxides,nitrogen oxides, water, oxygen, nitrogen, or other gases. Gases can alsobe mixtures. Common reaction products include treated hydrocarbon,hydrogen, ammonia, hydrogen sulfide, carbon dioxide, carbon monoxide,water, and other gases.

A widely-used example of a multi-phase vessel is a hydro-treating vesselfeeding both a liquid hydrocarbon, or oil, phase containing variousundesired sulfur species and a gas phase containing hydrogen. Thesephases are passed over active sites 40 contained in element beds 120. Adesirable reaction of hydro-treaters can be to react the hydrogen gasphase with the undesirable sulfur species in the oil phase at the activesite 40. The desirable reaction produces a sulfur-free hydrocarbon andhydrogen sulfide. The hydrogen sulfide is a reaction product, dissolvedin the liquid phase. In this example, as the desirable reaction isrepeated, hydrogen can be depleted from the liquid phase and hydrogensulfide can build up in the liquid phase. Gas exchange is desired toincrease the concentration of dissolved hydrogen gas in the liquid oilphase and simultaneously reduce the dissolved hydrogen sulfide gas fromthe liquid oil phase, as shown in FIG. 6B. The gas exchange depends onthe interfacial surface area between the liquid oil phase and the gasphase. The more thoroughly mixed the phases, the higher the surface areabetween them resulting in a higher rate of gas exchange. A high degreeof mixing is desirable. Example hydro-treaters typically operate astrickle bed reactors having temperatures ranging between 200 and 800degrees Fahrenheit and pressures ranging between 200 and 2,000 psi.Trickle bed reactors are multiphase reactors that contain fixed beds ofsolid elements and fluid phases that flow co-currently through thereactor.

Henry's Law (see William Henry, 1803) states that the mass of adissolved gas in a given volume of solvent at equilibrium isproportional to the partial pressure of the gas. In the conventionalhydro-treating example, to counteract the loss of liquid-gas surfaceinterface and to encourage the diffusion of hydrogen into the oil,hydrogen must be present in flow rates 3 to 5 times larger than the flowrate of oil entering the vessel 100. If 200 standard cubic feet ofhydrogen per barrel of oil are required for conversion, 600 to 1000standard cubic feet of hydrogen per barrel of oil needs to be fed to andcirculated within the vessel 100. The fluid feed phases are mixed atpoints of introduction into the vessel 100 or beds 120 by hardware knownas mixers, quenches, and/or distributor trays to allow gaseous hydrogendiffusion into the oil. Depending on vessel 100 pressure, temperature,and hydrogen purity, the maximum solubility of hydrogen in the oil isbetween 50 and 100 standard cubic feet per barrel of oil. The hydrogenand sulfur species in the diffused oil phase can interact with theactive sites 40 to perform the desired desulfurization reactions. Thesereactions create hydrogen sulfide as a recoverable by-product. Below thehardware known as mixers, quenches, and/or distributor trays, and abovethe element beds 120, top bed material 170 can be used for capabilitiescomprising filtration, distribution, and/or hold down.

A trickle bed reactor is a multi-phase vessel 100 configuration. Theco-current flows of liquid and gas through the reactor allow interactionof gas components with the liquid phase. Element beds 120 installed inthe vessel 100 can provide new and surprising advantageous reactorperformance including improvements in gas phase diffusion, reactioneffectiveness, hydrogen utilization and reaction product production andrecovery. When element beds 120 are packed into a trickle bed vessel,they have a packing efficiency and coordination number. Packingefficiency is defined as the volume percent of a space occupied by anelement bed 120. The coordination number is the number of contact pointsany element 125 has with the elements 125 that surround it. In general,as the packing efficiency increases so does the coordination number. TheKepler Conjecture (see Johannes Kepler, 1611) states that no arrangementof equally sized spheres filling space has a greater average densitythan that of the “cubic close packing.” The cubic close packing is ahighly ordered state and unlikely to be achieved unless spheres areplaced by hand. The coordination number for cubic close packing ofspheres is 12. The loading process in these vessels 100 is largelyrandom, but can be controlled to vary the degree of packing efficiencyand contact points between elements 125. Highly ordered close packing isnot probable in these loadings and coordination numbers can be less thanthe maximum. It is desired to increase the packing efficiency to have asmany elements 125 as possible in the vessel 100. However, hydrodynamicconstraints, e.g., differential pressure between phases, can limit theallowed packing efficiency. The depths of the loading can be anywherefrom approximately a few inches to 100 feet. These are conventionallyloaded as one element bed 120, with elements 125 of varying shapes andsizes, but are typically similarly loaded. Deeper element beds 120 aregenerally used to add cycle time and to improve the conversion which canbe achieved during operation. Diffusion of gas phase materials into theflowing liquid phase material can depend on the rate of diffusion asdetermined by elemental composition plus vessel 100 temperature,pressure and boundary layer issues governing the contact of gas andliquid species.

Liquid and gas phase flows will have superficial velocities defined bythe volumetric flow rate of these phases divided by the cross-sectionalarea of the process vessel 100. Actual liquid and gas phase flowvelocities can have local velocity variations which range from near zeroto over four times the calculated superficial liquid flow velocity.Additionally, density differences between liquid and gas phases exist.In part, this is what can lead to liquid and gas phase separation andreduced interfacial surface area between the phases.

“Liquid hold up” is a portion of the volume within the interstitialspaces between the elements 125. Liquid hold up can occur wherever theinterstitial liquid flow velocity is zero or near zero. Liquid flowvolume can be considered stagnant in these parts of the element bed 120.Typical liquid hold up in element beds 120 is in the range of 20%-40% ofthe interstitial space between the elements 125 and occurs in locationswhere the elements 125 are touching one another.

When element beds 120 are packed or loaded, they can be randomly packedand not in a highly ordered state. In this randomly packed stateapproximately 12 or less elements 125 contact any single element 125.The number of contact points can limit the pathways liquid can takebetween elements 125.

Important properties related to the behavior of liquid and gas phaseflow in a trickle bed reactor are determined by the properties of theelement beds 120 themselves. These properties are packing efficiency,void space diameter, and liquid hold up volume. Packing efficiency isdefined as the percent of the element beds 120 which fill a given space.Typical packing efficiencies for element beds 120 are in the range of55% to 65%. Typical space not filled by element beds 120 is, therefore,35% to 45%. This space is herein called “void space.” Higher packingefficiency allows for higher mass loadings of elements 125 into thevessel:void space %=100%−packing efficiency %

The void space in the element bed 120 also affects the range of liquidhold up the element beds 120 can achieve. With the packing efficienciesdescribed, liquid hold up can be in the range of 7%-18% of the elementbed 120 volume.

Void space diameter can be taken as the average size of the void spaceswhich are developed by packing the element beds 120. One way tocharacterize the expected void space diameter of a packed element bed120 is to use hydraulic diameter. Hydraulic diameter is defined by:

$D_{h} = \frac{4 \star {\frac{1 - p}{p}D_{e}}}{6p}$

Where D_(h) is hydraulic diameter, D_(e) is the nominal diameter of theelements 125, and p is the packing efficiency. For an element bed 120 ofnominally ⅛ inch (3.17 mm) sized elements 125 with a packing efficiencyof 60%, the hydraulic diameter is 2.34 mm or about ˜73% of the element125 diameter. For an element bed 120 of nominally sized 1/20 inch (1.27mm) sized elements 125 with a packing efficiency of 60%, the hydraulicdiameter is 0.94 mm, which is again ˜73% of the element 125 diameter.The hydraulic diameter can be taken as an approximate estimation of theaverage diameter of the void space between elements 125, called the voidspace diameter.

Liquid hold up volume can be related to void space diameter and packingefficiency. Void space diameter controls the efficacy of liquid hold upwith smaller void space diameters allowing a higher liquid hold up.Packing efficiency can also influence the amount of liquid hold up. Thehigher the packing efficiency, the lower the total liquid hold up. Asthe void space diameter shrinks, the liquid hold up in the void spacecan become driven by capillary action (see Leonardo da Vinci, c. 1500,see Robert Boyle, 1660). Capillary action occurs when the adhesion tothe surfaces of a material is stronger than the cohesive forces betweenthe liquid molecules or even the transportive forces on the liquidmolecules. The surface tension between the liquid and solid acts to holdthe surface intact. In the case of porous beds and porous bodies,adhesion of liquid to the surfaces of materials can cause a force on theliquid which acts to keep the liquid in contact with the solid. Due tothese, capillary action can increase the liquid hold up of material.Materials with high capillary action typically have high surface area tovolume ratios.

While higher liquid hold up improves the surface area and contactbetween the fluid phases and solid Elements, this is typically anundesirable property in trickle bed processing where intimate contactbetween liquid and gas phases components is important. Small void spacediameters can drive up liquid hold up while eliminating void spaceavailable for gas flow. It is more advantageous to have trickle bedproperties which allow for thin films 35 across the elements 125 inorder to maximize the interaction between the liquid and the gas. Atypical “thin film” 35 is comprised of a region of liquid phasepartially bound by a solid phase with a free surface where the liquidphase is exposed to a gas phase and the liquid phase travels on thesurface of the solid phase. Small void space diameters can encourageliquid hold up and, in the case of elements 125, contribute to thecollapse of thin films 35. It is desirable for a trickle bed reactor tosustain thin films 35. The gas is then able to flow over and interactwith the thin film 35 of liquid. Thin films 35 advantageously lead tohigher liquid surface areas with higher liquid-gas interface enablinggas exchange and, therefore, availability for reaction with elements125. But as discussed above, conventional trickle bed reactor thin films35 are typically not hydro-dynamically stable and can eventuallycollapse. Due to this instability, high liquid-gas interface surfacearea is difficult to achieve and maintain.

One advantageous method to overcome the necessity of high liquid-gasinteraction is to provide the ability to pre-mix and then distribute theliquid and gas onto the element bed 120. Conventional vessels canprovide initial mixing of the fluid phases by using “fabricatedengineered mixer equipment” or “distributor trays” installed tofacilitate mixing and distribution of fluid phases. This can also beaccomplished by way of one or more fabricated engineered distributiontrays or vapor phase mixers installed downstream of vapor injection.Such engineered mixer equipment is typically used to promote diffusionof hydrogen into oil, creating a reactant-rich liquid. Engineered mixerequipment can be complex, difficult and expensive to design, fabricate,install, operate and maintain. Installation, operation and maintenancerequires that the equipment is secured and aligned to be perpendicularto the flow of streams within the vessel 100. Additionally, theinstallation of such devices can take up 3 to 10 feet of vessel 100depth, space where there are typically no elements 125 installed. Aproperly installed and operated distributor tray can provide a highdegree of initial bed wetting and good liquid-gas-solid interaction atthe top of the element bed 120. Improperly installed and operateddistributor tray can ensure poor bed-wetting and top bed 170interaction. Such devices including trays and quench nozzles can beinstalled in the middle of the vessel 100.

This high liquid-gas surface area provided at the top of the element bed120 becomes reduced as the fluid phases go deeper into the element bed120. Regions of limited to no interaction between liquid and gas phasestake shape. This low interaction creates undesirable regions of reducedliquid-gas surface interface, decreasing the diffusion rate between thetwo fluid phases. The decreased diffusion rates can lead to reactantstarvation. Reactant starvation develops where one or more gas reactantcomponents are consumed in the diffused fluid state faster than they canbe replenished from the surrounding gas phase. The reduced diffusionleads to the development of a reactant-lean liquid. The growing presenceof liquid-gas separation and reactant starvation can: increase thehydrogen flow rate required to sustain gas exchange; decrease theeffectiveness of the element beds 120; reduce overall vessel 100performance due to a reduction in desired reactions; and increase thepresence of coking reactions.

In trickle bed vessels 100, one or more desired gas components can bedepleted from the liquid phase due to reaction between: undesired liquidspecies reactants, diffused gas phase reactants, and active sites 40.

Reaction products accumulate in the diffused liquid phase as a result ofthe same reactions leading to a product-rich liquid. For efficientreaction, one or more desired gas phase reactant components must bereplenished into the one or more diffused liquid phases and the one ormore reaction products removed from the diffused liquid phases. It isdesirable for the reactant-lean, product-rich liquid to transition to areactant-rich, product-lean liquid. The separation of liquid and gasphases caused by deterioration of the trickle bed reactor performancereduces the surface area between the phases and disables thesefunctions. This can result in reduced reaction kinetics because thedesired gas phase reactants are not available for reaction and thereaction products remain dissolved in the fluid and interfere with thedesired reactions between reactants.

In the hydro-treating example, if the hydrogen reactant becomes limited,other reactions can take place in the absence of hydrogen. In general,these other reactions are referred to as coking and can cause harm tothe effectiveness of the element bed 120. Coking takes several forms,each form resulting in a buildup of difficult species that can blockactive sites 40 on the element beds 120.

Coking occurs due to molecular cracking, olefinic polymerization, andaromatic polymerization. Aromatic polymerization refers to the growth ofpolycyclic aromatic compounds. Once these molecules grow large enoughthey are able to deposit on the surface of active sites 40. These areundesired products. Olefinic polymerization refers to the growth ofunsaturated paraffin compounds. These grow to be large and block activesites 40. Molecular cracking refers to the continual breaking ofhydrocarbon chains. As these chains are broken, if hydrogen is notpresent in sufficient amounts, unsaturated molecules are formed andactive sites 40 are blocked. Coking is a major contributor to elementbed 120 deactivation and can lead to the “death” of the active sites 40,requiring the vessel 100 to be shut down and the elements 125 to beremoved and/or exchanged. It is desirable to reduce the deactivationrate caused by coking.

The performance of reactions in the one or more conventional elementbeds 120 can change with the depth of the beds. At the top of theupper-most element bed 120, near the properly installed, operated andmaintained engineered mixer equipment 190, trickle bed reactorperformance is high and coking reaction rates may be minimal. As thefluid phase goes deeper into the bed, element bed 120 performancedeteriorates: the surface area between the liquid phase and gas phasedecreases, the dissolved gas in the liquid is consumed, reactantstarvation ensues, the coking reaction rates can increase, and theactive site 40 performance drops. The higher the concentration ofundesirable species in the liquid phase, the faster reaction starvationcan develop. In the case of a hydro-treater intended to remove sulfurspecies, the overall lower rates of desired reactions result in higherproduct sulfur content, higher operating temperature, and shorter cyclelengths.

Processing conditions can be adjusted to respond to element bed 120deactivation to keep the processing vessel 100 producing desirablereactions. Responses to element bed 120 deactivation can requireincreased element bed 120 temperature and/or reduction in element bed120 feed rate. Increase in temperature serves to increase reaction ratein the vessel 100 to make up for lost activity. Reduction in feed ratereduces the required reaction rate. Continued adjustments or responseswill fail as temperature increase eventually will exceed vessel 100operating constraints and feed rate reduction results in economicallyunfavorable operation. Steps taken at this point include vessel 100shutdown and steps to make element bed 120 replacement.

Disclosed are novel effects which increase the rate of gas exchange,done by exchange layers 140, into and out of two or more fluid phasecomponents in one or more vessels 100 containing one or more elementbeds 120 which facilitate conversion between the reactants contained inthe fluid phases. Steps which create these include one or more: vessels100 equipped with improved exchanged gas facilities; diffused fluidphases with improved interactions; exchange layers 140 which improvereactant replenishment via thin film 35 diffusion; reduceduncontaminated active sites, including coke, contained in element beds120; and reaction products escaping the reaction zone quickly andefficiently.

Increased reactant-rich liquid phases remove gas exchange limitationsand can increase the element bed 120 reaction rate. Both of theseimprovements can lead to benefits such as lower operating temperature,increased throughput, and reduced gas circulation. Improved availabilityof the gas phase components in the liquid phase can also serve to reducethe rate of a harmful side reaction, like coke formation, on or in theelement beds 120. This helps mitigate one of the most common causes forvessel 100 shutdown and increases the capability of an element bed 120to perform its desired reactions.

Additional disclosed benefits from improving gas exchange would be theability to achieve higher conversion rates for a constant set ofoperating conditions (e.g. temperature, pressure, and feed rate). Forsimilar inlet concentrations of undesired liquid species at constantoperating conditions, improved gas exchange would provide lowerconcentrations of undesired species in the product phases of such avessel 100.

The use of exchange layers 140 can have surprising and unexpectedresults. Such results can have positive impacts on the operation of aprocessing vessel. Exchange layers 140 which enable a low rate of cokeformation can result in a more constant or nearly constant inlettemperature over time. Since the inlet temperature is not being raised,the process vessel 100 is able to operate for a longer period of time orprocess more feed before a shutdown is required. Furthermore, operatingat lower temperatures also enables improved rates of aromatic saturationand exchange layers 140 could be useful in helping to improve aromaticsaturation on the basis of both hydrogen availability and a reduction inoperating temperature. Even further, exchange layers 140 can enableconversion of compounds which can require multiple steps to remove theundesired species. As an example, some sulfur species are known as“hindered”, where aromatic rings block the removal of the hinderedsulfur from the hydrocarbon. The aromatic ring must first undergo asaturation reaction to become a naphthene, followed by the sulfurremoval step. The aromatic saturation step unblocks the sulfur moleculeand both reactions must proceed in order, otherwise the naphthene canconvert back to an aromatic, once again hindering the sulfur removal.

Another surprising and unexpected result of using an exchange layer 140would be a reduced amount of carbon build up on elements 125 at or belowthe level of the exchange layer 140. In element beds 120 where hydrogenconsumption is high, once the liquid phase becomes a “reactant-lean”liquid phase, coking formations take place and deposit carbon on theelements 125. The buildup of carbon harms the process vessel operationand can make it difficult to unload the elements 125 from the processvessel 100. The carbon build up fuses the elements together 125 makingunloading difficult. Use of exchange layers 140 at these locations canreduce carbon deposition. In place of coking, desired reactions canoccur. This result could be observed during the unloading of such aprocess vessel 100. The elements above the exchange would be filled withcarbon and be fused together, where the exchange layer 140 and theelement bed 120 below it would have reduced amounts of carbon and theelements 125 would be free flowing.

In certain illustrative embodiments, as shown in FIG. 1 and FIG. 2,vessel 100 can include one or more exchange layers 140 containing mediawhich can facilitate gas exchange between fluid phases in the vessel100. Vessels 100 can be one vessel or multiple vessels functioningtogether. Exchange layers 140 can avoid starvation of fluid reactants.Exchange layers 140 can advantageously facilitate the production ofreactant-rich, product-lean liquid phases. In certain illustrativeembodiments, the performance of exchange layers 140 can be dependent onthe location and depth of the media, the size and structure of themedia, the surface area of the media, the positions of the media and/orthe positions and compositions of the fluid phases in the vessel 100.Exchange layers 140 can be positioned relative to element beds 120.Exchange layers 140 can be positioned upstream of element beds 120 tofacilitate the diffusion of fluid phases entering the element beds 120.Exchange layers 140 can also be positioned downstream of element beds120 to facilitate diffusion of fluid phases for processing in downstreamelement beds 120. Exchange layers 140 can be installed along withdistributor trays and/or injection ports that may also be in the vessel.Exchange layers 140 can be installed below top bed 170 material prior toentry into the element bed 120 or can also be installed at the top of abed within vessel 100. Exchange layers 140 can, but do not need to, spanthe diameter of the vessel 100. Exchange layers 140 could be pocketedthroughout the vessel 100, whereby they do not span the diameter of thevessel 100, but still provide functionality in the region where they doexist.

In certain illustrative embodiments, the disclosed media in exchangelayers 140 can include one or more zones containing collector media 20and one or more zones containing releaser media 30. The interaction ofthese media with the liquid and gas phases helps to advantageouslyfacilitate the exchange of liquid and gas phase components in the vessel100. As illustrated in FIG. 3A, the collector media 20 and the releasermedia 30 can enable gas exchange for co-current flow of the phaseswithin exchange layer 140. As illustrated in FIG. 3B, the collectormedia 20 and the releaser media 30 can enable gas exchange and act as atreating bed for co-current flow within exchange layer 140. In certainillustrative embodiments, collector media 20 utilize liquid hold up andcapillary action to facilitate one or more processes occurring withinvessel 100. This can occur within exchange layer 140, whereby the liquidhold up is increased for a given region of volume within one or morecollection zones 22 of collector media 20. The collection zones 22provide a localized region in collector media 40 where the flowingliquid phase can be collected or held, hereinafter “liquid collection”.Once liquid collection is maximized within the collection zone 22, anyaddition of liquid volume can cause an outflow of liquid from thatregion. Collector media 20 can be shaped so as to maximize or minimizethe size of the liquid collection region in collection zone 22 and allowthe outflow of liquid from the liquid collection 22. The filled liquidcollection 22 also allows gas phase flows to bypass the collector media20 and interact with the downstream releaser media 30.

The presently disclosed subject matter provides surprising andunexpected results as compared to previously used technologies. Thedescribed liquid hold up can be detrimental to process vessel operationdue to the inherent forces which promote separation of liquid and gasphases.

In certain illustrative embodiments, exchange layers 140 avoid thisproblem by creating a region of high surface area by providing collectormedia 20 and high surface area releaser media 30 adjacent to andsurrounding the collector media 20, as shown in the illustrativeembodiments of FIG. 4 and FIG. 5A. This region enables the outflow ofliquid from collector media 20. Capillary action can draw and holdliquids into collector media 20. Collector media 20 facilitated byliquid hold up and capillary forces deliver uniform liquid flow acrossthe region of high surface area.

In certain illustrated embodiments, the volume flow of liquid ontoreleaser media 30, a high surface area solid, enables formation of athin film 35 on an outer surface of releaser media 30, as shown in FIG.6, which enhances the mixing of liquid in the thin film 35 and gaspassing over the thin film 35. This enhanced mixing and this surfacearea can enables exchange of gas phase components into the liquid phase,creating reactant-rich liquid phases. This enhanced mixing and thissurface area enables dissolution of undesired gas phase components outof the liquid phase, creating product-lean liquid phases. Generatingthis high surface area surrounding collector media 20 and enablingoutflow of liquid with thin film 35 formation is a function of releasermedia 30, in certain illustrative embodiments.

In certain illustrative embodiments, collector media 20 and releasermedia 30 can be high geometric surface area media, including porousmedia. Porous media are defined as a solid with pores which enter intoand/or through the media. The porous media can include reticulates,honeycomb monoliths, macro-porous materials, fissured material,agglomerates of particle packing, and fibrous mesh. These porous mediacan be shaped as spheres, cylinders, rings, briquettes, ellipsoids,prisms, cubes, parallelepipeds, ortho-topes, saddles, wagon wheels,medallions, lobed extrudates and the like. Porous media can have surfacefeatures including asperities such as polyps, fibrils, filaments, hairs,ridges, lobes, troughs, fins, and the like. Porous media can bemetallic, ceramic, polymeric or combinations of these. Porous media canbe oxides, nitrides, carbides or the like.

In certain illustrative embodiments, active sites 40 can be added toreleaser media 30. In certain illustrative embodiments, releaser media30 can be elements 125. In certain illustrative embodiments, releasermedia 30 can be inert. In certain illustrative embodiments, collectormedia 20 can be converted into elements 125 by adding active sites 40 tothe collector media 20. In certain illustrative embodiments, collectormedia 20 can be inert.

In certain illustrative embodiments, collector media 20 are capable ofcontaining or holding liquid phases. Collector media 20 can haveindividual sizes ranging between 12 and 200 millimeters. Collector media20 can have pore pathways having diameters ranging from 1 micron to 20millimeters. The collector media 20 internal void space, composed of thepore pathways, can make up 20% to 95% of the volume of the collectormedia 20. Collector media 20 can have internal void space that rangesfrom 100 to 6,000 square feet per cubic foot of collector media 20.Within the exchange layer 140, collector media 20 can be packed toachieve 30% to 70% packing efficiency. By controlling the pore sizes,collector media 20 can achieve up to 100% liquid collection in theirinternal void space. Liquid collection can be determined by multiplyingthe packing efficiency and the internal void space. For the packingefficiency and internal void space described, collector media 20 liquidcollection can be in the range of 6%-66.5% of the exchange layer 140volume. This range provides the ability to control liquid collection toa much greater degree. A preferred amount of liquid collection would bein the range of 20% to 66.5% of the exchange layer 140 volume,surpassing the liquid hold up of previously mentioned elements 125. Thiscan be achieved by any combination of the packing efficiency andinternal void space described.

In certain illustrative embodiments, collector media 20 can disperseliquid phases within vessel 100 to releaser media 30. For example, whenthe collector media 20 are completely filled with liquid, gas phasephases can bypass collector media 20. In other illustrative embodiments,the collector media 20 are partially filled with liquid, gas phases canmove through collector media 20, co-current with the liquid phase.

In certain illustrative embodiments, releaser media 30 can receiveliquid release from the collector media 20. Releaser media 30 can havean interstitial void space, defined by the volume consumed by porepathways, which is permeable to the gas phase fluids. Coupled withformation of the thin film 35 as a liquid on the releaser media 30, gasflow in the interstitial void spaces can create an opportunity for ahigh degree of mixing and liquid-gas exchange on the thin film 35,improving gas exchange. Releaser media 30 can be equal to or smallerthan the size of the collector media 20 they surround, to fit into thespace created by the collector media 20. In certain illustrativeembodiments, the releaser media 30 sizing would be 1/32″ to ½″. Releasermedia 30 can be the same shape or a different shape than collector media20. In certain illustrative embodiments, releaser media 30 can have asmany touch points as possible for liquid release from the collectormedia 20 to the neighboring releaser media 30. This can be done bychoosing releaser media 30 sizing small enough to increase contactpoints and surface area, but large enough that both liquid and gas phaseare able to flow co-currently through the space surrounding the releasermedia 30 and across the thin film 35 surfaces of the releaser media 30.Additionally, the shape of the releaser media 30 will influence thesurface area and void space shape.

In certain illustrative embodiments, releaser media 30 can have sizesranging from 800 microns to 12.7 millimeters. Releaser media 30 can havegeometric surface areas ranging from 60 to 1000 square feet per cubicfoot of releaser media 30. Releaser media 30 can also be packed withinthe spaces between the larger collector media 20 so as to surround thecollector media 20. Releaser media 30 can achieve a packing efficiencyof >50% within the spaces surrounding the collector media 20. Contactareas between releaser media 30 and collector media 20 can act asrelease points to receive liquid from neighboring collector media 20. Itis desirable to have packing that achieves the greatest number ofreleaser media 30 contact release points on the collector media 20 outersurface. In one preferred embodiment releaser media 30 can have sizingfrom 1/14th to ¼th the size of collector media 20. In certain otherillustrative embodiments releaser media 30 can have sizing less than1/14th the size of collector media 20. In yet another illustrativeembodiment releaser media 30 can have sizing greater than ¼th the sizeof collector media 20. Also, at least twenty contact points are desiredbetween each collector media 20 and the releaser media 30, in certainillustrative embodiments. For example, FIG. 14A is a three dimensionalview and FIG. 14B is a three dimensional cross-sectional view ofreleaser media 30 surrounding collector media 20 in a manner that wouldprovide at least twenty contact points therebetween. Due to the natureof low volume outflow and the described high surface area available forthe liquid phase phases exiting the collector media 20, the liquid cantravel along the releaser media 30 as thin films 35. Releaser media 30have exposure to gas phases to encourage the diffusion of gas componentsinto the liquid due to these thin films 35. During contact with thereleaser media 30, the amount of gas exchanged into the thin film 35liquid phase can be increased due to the higher rate of diffusion causedby the thin film 35 high surface area.

Collector media 20 and releaser media 30 work together in order toimprove the liquid-gas interfacial surface area. For certain pore sizeswithin the collector media 20, liquid hold up and capillary forces candevelop, providing liquid collection within the media. At maximum liquidcollection, excess liquid is released from the collector media 20 to thereleaser media 30 where gas exchange is provided through the releasermedia 30.

Conventional element beds 120 without exchange layers 140 can provide ahigh surface area structure, but can lack the stability to generatesustained thin film 35 conditions. Hence, the trickle bed flow regimedevolves into a low liquid-gas surface interface area, disabling highinteraction between the liquid and gas phases. Disclosed collector media20 provide void space for a high volume of liquid collection, a smallpore size for a capillary force to slow liquid flow and can allow liquidaccumulation, and can be permeable enough to provide organized releaseof liquid onto the releaser media 30.

In certain illustrative embodiments, the pore sizes of a collector media20 are less than the size of an individual releaser media 30 to keep thereleaser media 30 out of the internal structure of the collector media20. In a preferred illustrative embodiment, collector media pore sizesare less than the void space diameter of releaser media 30 to encourageliquid collection in the collector media 20 and allow liquid outflowonto the releaser media 30.

In certain illustrative embodiments, the collector media 20 have porevolume within their bodies. The pore volume is of a pore size which ispermeable to liquid phases, but is smaller than the void space diameterof the surrounding releaser media 30. As a result, collector media 20can have a higher liquid collection capability than that of thesurrounding releaser media 30. As the collector media 20 reach theirmaximum liquid collection, as determined by the internal void space ofthe collector media 20, the filled collector media 20 will releaseliquid in the direction of gravity. The collected liquid can bepreferentially released to any downstream media (i.e., releaser media30) which is contacting the downstream surface of the upstream media(i.e., collector media 20) at as many interface points as possible. Thiscan create an opportunity for release of liquid to the neighboringpacked bed of releaser media 30.

In certain illustrative embodiments, this releases thin films 35 withhigh surface area to develop on the surface of the releaser media 30. Asprovided by Ficks' laws, the higher surface area of the thin films 35will enable improved transfer rate between the liquid and gas phases. Asa result, desired feed stream gas components, continually depleted inthe diffused liquid phase, can have an improved transfer rate into thediffused liquid phase, while reaction product gas components, whichbuild up in the diffused liquid phase, can have an improved transferrate out of the diffused liquid phase.

In certain illustrative embodiments, to maximize diffusion it isdesirable to have high interfacial surface area between the liquid andgas phases at the interface of exchange layers 140 and element beds 120in the vessels 100 in order to create sufficient exchange between thephases. The combined action of collector media 20 and releaser media 30contained in an exchange layer 140 serves to provide high interfacialsurface area between the liquid and gas. That high surface area providesimmediate improvement of gas exchange with the diffused liquid phasewithin the exchange layer 140, but also permeates into the local areadownstream of the exchange layer 140 providing continued ability of gasexchange with the diffused liquid phase contacted with the element bed120. The use of exchange layers 140 can be repeated further downstreamat any depth where the interfacial surface area has degraded or thedissolved gas consumption outpaces the diffusion rate of the gas phaseinto the liquid phase to provide regeneration of high surface areainterface and exchange capability. This could lead to varying layerdepths of exchange layers 140 or varying depths of element beds 120between exchange layers 140 depending on the processing needs andconditions.

In certain illustrative embodiments, the one or more exchange layers 140can be composed of both collector media 20 and releaser media 30. Thecollector media 20 and releaser media 30 can be in alternating layers,as shown in FIG. 13, as stratified structures, or combinations thereof.In certain illustrative embodiments, the collector media 20 and releasermedia 30 would fill the cross-section of the processing vessel 100 andhave depths of 3″ to 12″.

In certain illustrative embodiments, the development of thin film 35 canbe within the collector media 20 themselves. This would allow gasexchange to occur in both the collector media 20 and any surroundingreleaser media 30, increasing the amount of time desirable feed steamgases would have to diffuse into the liquid and undesirable productgases would have to diffuse out of the reaction zone. The pore diameterfor such collector media 20 would be between 100 microns and 30millimeters. In this embodiment, the pore diameter of the collectormedia 20 can be larger than the pore diameter of the surroundingreleaser media 30.

In certain illustrative embodiments, as shown in FIG. 12, exchangelayers 140 can be positioned relative to the top-bed 170 of the vessel100 and the feed entry points. Vessel 100 can also include engineeredmixer equipment 190 such as a mixer or distribution tray which canperform as designed or can under-perform in the event of faultyoperation. Exchange layer 140 can be positioned immediately downstreamof such engineered mixer equipment 190 and immediately upstream of themost upstream element bed 120. Exchange layers 140 can also bepositioned relative to intermediate feed points 180 on vessel 100, whichcan be quench ports or distribution trays, typically used to supplementfeed of gas phases. Exchange layer 140 positioning can be such that voidspaces are provided between such equipment or bed layers.

In prior art vessels, gas exchange ability can degrade in conventionaltrickle bed flow regimes and initial flow can be degraded as well, asillustrated in the “prior art” vessel in FIG. 11. In certainillustrative embodiments, this degradation can be mitigated via aprocess of collection and release to be repeated within a singleexchange layer 140 within vessel 100, or by periodically repeating orstrategically placing a plurality of exchange layers 140 throughout thebed or vessel 100 or to have an entire bed or vessel 100 comprised ofexchange layers 140, as illustrated in the vessel 100 on the right inFIG. 11, whereby gas exchange capability is improved.

In certain illustrative embodiments, exchange layers 140 can bepositioned relative to the position of elements 125 within the vessel100. Elements 125 can be positioned downstream of the exchange layer140. The depth of elements 125 can be from 6 inches to 90 feet dependingon: the characteristics and properties of the exchange layers 140; thenature of the fluid phases; the performance of the thin film 35 inproducing trickle bed flows; and the absence of coking in element bed120.

In certain illustrative embodiments, disclosed exchange layers 140 allowelements 125 to facilitate increased performance of vessel 100operations by promoting gas component mixing and diffusion. Improvedrates of gas component exchange mean less coking and more gas componentsavailable for reaction. Additionally, due to the reactant-rich liquidphase, dispensed by the releaser media 30, the expected reaction ratebetween the diffused gas and undesired species contained at active sites40 are increased, thus making better use of the element beds 120 in thevessel 100.

Exchange layers 140 could also be advantageously utilized inapplications where vessels are constrained by low gas streamavailability or low gas stream operating pressures or where hydrogeneconomics greatly favor conserved operations. Lower operating pressuresresult in lower exchange of gas components. As Ficks' laws demonstrate,lower concentrations will reduce the rate of gas diffusion into theliquid phase. Exchange layers 140 can improve the rate of diffusion intothe liquid phase and can help conserve hydrogen circulationrequirements. Higher availability of gas phase components to thediffused liquid phase allows for lower vessel 100 operating temperaturesor a slowing vessel 100 temperature increase, increasing the amount offeed the active sites 40 and the vessel 100 can process, and extendingthe amount of time the elements 125 can be on-oil. Additionally, theprocessing vessel 100 can have more feed flexibility and can be able tohandle a wider variety of undesired species. An advantage of such asystem is the ability to arrange locations of exchange layers 140dependent on the gas component consumption occurring on the element beds120. For example, in a hydro-cracking unit which is consuming 2000SCF/BBL within a total depth of 60 feet (33 SCF/BBL/FT), may requiremore frequent or large depth exchange layers 140 compared to a Naphthahydro-treater which is consuming 100 SCF/BBL within a total depth of 30feet (3.3 SCF/BBL/FT). In the hydrocracker example, exchange layers 140can be used in conjunction with a gas quench to enable both cooling ofthe liquid stream and mixing of the gas and liquid simultaneously.

In certain illustrative embodiments, the collector media 20 can be asingle collector pane, as shown in FIG. 9 and FIG. 10, which fills thecross-section of the vessel 100. Additionally, this collector pane canhave a plurality of perforation holes 25 formed in its cross-section inorder to avoid a build-up of gas pressure on the upstream side of thecollector pane. The perforation holes 25 can be filled with releasermedia 30, in certain illustrative embodiments. In certain illustrativeembodiments, the collector pane can be made up of a plurality ofinterlocking or snug-fitting parts in order to enable installation anddisassembly during the loading and unloading of the vessel 100. Thecollector pane can be, in certain illustrative embodiments, 3″ to 12″ indepth. The collector pane perforation holes 25 can be, in certainillustrative embodiments ⅛″ to 3 feet in diameter. The concentration ofperforation holes 25 can be from a single hole 25 across thecross-section of the vessel 100 up to one hole 25 per square inch. Incertain illustrative embodiments, collector panes could be stacked ontop of each other or used in a stratified collector media 20/releasermedia 30 orientation as previously described herein

As used herein, the phrase “at least one of” A, B and C shall mean onlyA, or only B, or only C, or any combination of A, B and C.

While the disclosed subject matter has been described in detail inconnection with a number of embodiments, it is not limited to suchdisclosed embodiments. Rather, the disclosed subject matter can bemodified to incorporate any number of variations, alterations,substitutions or equivalent arrangements not heretofore described, butwhich are commensurate with the scope of the disclosed subject matter.

Additionally, while various embodiments of the disclosed subject matterhave been described, it is to be understood that aspects of thedisclosed subject matter may include only some of the describedembodiments. Accordingly, the disclosed subject matter is not to be seenas limited by the foregoing description, but is only limited by thescope of the claims.

What is claimed is:
 1. A method of treating a reactant-lean liquid phasein a process vessel, comprising: passing the reactant-lean liquid phaseand a gas phase co-currently through an exchange layer in the processvessel, wherein the gas phase comprises a reactant; and diffusing atleast some of the reactant from the gas phase into the reactant-leanliquid phase in the exchange layer to form a reactant-rich liquid phase,wherein the exchange layer comprises a plurality of collector media anda plurality of releaser media, and wherein the collector media compriseporous solid materials capable of collecting the reactant-lean liquidphase within the collector media, and wherein the releaser mediacomprise solid materials having a thin film formed on an outer surfacethereof that is capable of facilitating contact and diffusion betweenthe reactant-lean liquid phase and the gas phase, and wherein the thinfilm is formed on the releaser media during processing as a result ofliquid released from the collected liquid phase.
 2. The method of claim1, wherein the process vessel s a trickle bed reactor.
 3. The method ofclaim 1, further comprising passing the reactant-rich liquid phasethrough a bed of porous solid elements following the exchange layer, theporous solid elements comprising at least one of catalysts, sorbents andreactants.
 4. The method of claim 1, further comprising performing atreating process in the process vessel to remove an undesired speciesfrom the liquid phase, wherein the treating process comprises at leastone of hydro-desulfurization, hydro-denitrogenation, hydro-cracking,hydrogenation, hydro-dearomatization, hydro-deoxygenation,hydro-demetallization, and isomerization.
 5. The method of claim 4,wherein the undesired species comprises at least one of sulfur,nitrogen, oxygen, aromatics, olefins, nickel, vanadium, iron, silicon orarsenic.
 6. The method of claim 1, wherein the reactant-rich liquidphase comprises at least one of naphtha, gasoline, kerosene, jet,diesel, gas oils, vegetable oils, animal tallow, and liquid water. 7.The method of claim 1, wherein the reactant diffused from the gas streaminto the reactant-lean liquid stream comprises at least one of methane,butane, propane, butalene, propylene, hydrogen, ammonia, hydrogensulfide, carbon dioxide, carbon monoxide, sulfur oxides, nitrogenoxides, water gas, oxygen, and nitrogen.
 8. The method of claim 1,wherein the releaser media comprise at least one of catalysts, sorbentsand reactants.
 9. The method of claim 8, wherein the size of thereleaser media is no more than one-fourth the size of the collectormedia.
 10. The method of claim 8, wherein each of the collector media inthe exchange layer has at least twenty contact points on its outersurface that are contacted by releaser media.
 11. A method of treating aproduct-rich liquid phase in a process vessel, comprising: passing theproduct-rich liquid phase and a gas phase co-currently through anexchange layer in the process vessel, wherein the product-rich liquidphase comprises a reaction product; and diffusing at least some of thereaction product from the product-rich liquid phase into the gas in theexchange layer to form a product-lean liquid phase, wherein the exchangelayer comprises a plurality of collector media and a plurality ofreleaser media, and wherein the collector media comprise porous solidmaterials capable of collecting the product-rich liquid phase within thecollector media, and wherein the releaser media comprise solid materialswhich are capable of facilitating contact and diffusion between theproduct-rich liquid phase and the gas phase, and wherein the releasermedia are no more than one-fourth the size of the collector media, andwherein each of the collector media in the exchange layer has at leasttwenty contact points on its outer surface that are contacted byreleaser media.
 12. The method of claim 11, wherein the process vesselis a trickle bed reactor.
 13. The method of claim 11, further comprisingpassing the product-lean liquid phase through a bed of porous solidelements following the exchange layer, the porous solid elementscomprising at least one of catalysts, sorbents and reactants.
 14. Themethod of claim 11, further comprising performing a treating process inthe process vessel to remove an undesired species from the liquid phase,wherein the treating process comprises at least one ofhydro-desulfurization, hydro-denitrogenation, hydro-cracking,hydrogenation, hydro-dearomatization, hydro-deoxygenation,hydro-demetallization, and isomerization.
 15. The method of claim 14,wherein the undesired species comprises at least one of sulfur,nitrogen, oxygen, aromatics, olefins, nickel, vanadium, iron, silicon orarsenic.
 16. The method of claim 11, wherein the product-lean liquidphase comprises at least one of naphtha, gasoline, kerosene, jet,diesel, gas oils, vegetable oils, animal tallow, and liquid water. 17.The method of claim 11, wherein the releaser media comprise at least oneof catalysts, sorbents and reactants.
 18. A method of treating areactant-lean, product-rich liquid phase in a trickle bed processvessel, comprising: passing the reactant-lean, product-rich liquid phaseand a gas phase co-currently through an exchange layer in the tricklebed process vessel, wherein the gas phase comprises a reactant; anddiffusing at least some of the reaction products from the reactant-lean,product-rich liquid phase into the gas phase and at least some of thereactant from the gas phase into the reactant-lean, product-rich liquidphase in the exchange layer to form a reactant-rich, product-lean liquidphase, wherein the exchange layer comprises a plurality of collectormedia and a plurality of releaser media, and wherein the collector mediacomprise porous solid materials capable of collecting the reactant-leanliquid phase within the collector media, and wherein the releaser mediacomprise solid materials having a thin film formed on an outer surfacethereof that is capable of facilitating contact and diffusion betweenthe reactant-lean, product-rich liquid phase and the gas phase, andwherein the thin film is formed on the releaser media during processingas a result of liquid released from the collected liquid phase.
 19. Themethod of claim 18, further comprising passing the reactant-rich,product-lean liquid phase through a bed of porous solid elementsfollowing the exchange layer, the porous solid elements comprising atleast one of catalysts, sorbents and reactants.
 20. The method of claim18, further comprising performing a treating process in the processvessel to remove an undesired species from the liquid phase, wherein thetreating process comprises at least one of hydro-desulfurization,hydro-denitrogenation, hydro-cracking, hydrogenation,hydro-dearomatization, hydro-deoxygenation, hydro-demetallization, andisomerization.
 21. The method of claim 20, wherein the undesired speciescomprises at least one of sulfur, nitrogen, oxygen, aromatics, olefins,nickel, vanadium, iron, silicon or arsenic.
 22. The method of claim 18,wherein the reactant-rich, product-lean liquid phase comprises at leastone of naphtha, gasoline, kerosene, jet, diesel, gas oils, vegetableoils, animal tallow, and liquid water.
 23. The method of claim 18,wherein the reactant diffused from the gas stream into thereactant-lean, product-rich liquid stream comprises at least one ofmethane, butane, propane, butalene, propylene, hydrogen, ammonia,hydrogen sulfide, carbon dioxide, carbon monoxide, sulfur oxides,nitrogen oxides, water gas, oxygen, and nitrogen.
 24. The method ofclaim 18, wherein the releaser media comprise at least one of catalysts,sorbents and reactants.
 25. The method of claim 24, wherein the size ofthe releaser media is no more than one-fourth the size of the collectormedia.
 26. The method of claim 24, wherein each of the collector mediain the exchange layer has at least twenty contact points on its outersurface that are contacted by releaser media.
 27. A trickle bed processvessel for treatment of a reactant-lean, product-rich liquid stream,comprising: an exchange layer comprising a plurality of collector mediaand a plurality of releaser media, wherein the exchange layer is capableof facilitating diffusion of one or more reactants from a gas phase intoa reactant-lean, product-rich liquid phase within the exchange layer toform a reactant-rich, product-lean liquid phase; and a treatment layerdownstream of the exchange layer comprising a bed of porous solidelements, the porous solid elements comprising at least one ofcatalysts, sorbents and reactants and capable of performing a treatingprocess to remove an undesired species from the liquid phase, whereinthe treating process comprises at least one of hydro-desulfurization,hydro-denitrogenation, hydro-cracking, hydrogenation,hydro-dearomatization, hydro-deoxygenation, hydro-demetallization, andisomerization, wherein the collector media and the releaser media arepacked within the exchange layer such that each of the collector mediahas at least twenty contact points on its outer surface that arecontacted by releaser media, and wherein the gas phase and thereactant-lean, product-rich liquid phase undergo co-current flow withinthe exchange layer, and wherein the collector media comprise poroussolid materials capable of collecting the reactant-lean liquid phasewithin the collector media; and wherein the releaser media comprisesolid materials having a thin film formed on an outer surface thereofthat is capable of facilitating contact and diffusion between thereactant-lean, product-rich liquid phase and the gas phase, and whereinthe thin film is formed on the releaser media during processing as aresult of liquid released from the collected liquid phase.
 28. Theprocess vessel of claim 27, wherein the releaser media comprise at leastone of catalysts, sorbents and reactants.
 29. The process vessel ofclaim 27, wherein the size of the releaser media is no more thanone-fourth the size of the collector media.
 30. The process vessel ofclaim 27, wherein the undesired species comprises at least one ofsulfur, nitrogen, oxygen, aromatics, olefins, nickel, vanadium, iron,silicon or arsenic, and wherein the reactant-rich, product-lean liquidphase comprises at least one of naphtha, gasoline, kerosene, jet,diesel, gas oils, vegetable oils, animal tallow, and liquid water, andwherein the reactant diffused from the gas stream into thereactant-lean, product-rich liquid stream comprises at least one ofmethane, butane, propane, butalene, propylene, hydrogen, ammonia,hydrogen sulfide, carbon dioxide, carbon monoxide, sulfur oxides,nitrogen oxides, water gas, oxygen, and nitrogen.